Disorder effects in Mn₁₂–acetate at 83 K

The structure of hexadeca-μ-acetato-tetra­aqua­dodeca-μ₃-oxo-dodecamanganese bis(acetic acid) tetrahydrate, [Mn₁₂O₁₂(CH₃COO)₁₆(H₂O)₄]·2CH₃COOH·4H₂O, known as Mn₁₂–acetate, has been determined at 83 (2) K by X-ray diffraction methods. The fourfold (S₄) molecular symmetry is disrupted by a strong hydrogen-bonding interaction with the disordered acetic acid mol­ecule of solvation, which displaces one of the acetate ligands in the cluster. Up to six Mn₁₂ isomers are potentially present in the crystal lattice, which differ in the number and arrangement of hydrogen-bonded acetic acid mol­ecules. These results considerably improve the structural information available on this molecular nanomagnet, which was first synthesized and characterized by Lis [Acta Cryst. (1980), B36, 2042–2046].

S1. Comment

The compound [Mn₁₂O₁₂(CH₃COO)₁₆(H₂O)₄]·4H₂O·2CH₃COOH, known as Mn₁₂-acetate, (I), is the prototype of a class of magnetic materials referred to as `single-molecule magnets' (Sessoli et al., 1993). The acronym reflects the exceedingly slow relaxation of the magnetization at low temperature (LT), which is reminiscent of bulk magnets. In (I), however, the slow magnetic relaxation has a purely molecular origin, as established by measurements in solution (Cheesman et al., 1997) and in polymer films (Eppley et al., 1995). It arises from the huge easy-axis magnetic anisotropy in the ground spin state (S = 10), and from the energy barrier (60 K) to be overcome for the reversal of the magnetization. In addition, due to the intrinsic quantum nature of the system, underbarrier tunnelling processes are possible which lead to characteristic steps in the hysteresis loops at LT (Friedman et al., 1996). \sch

Compound (I) was first synthesized and structurally characterized by room temperature (RT) methods in 1980 (Reference?). The crystal lattice (tetragonal space group I4) comprises [Mn₁₂O₁₂(CH₃COO)₁₆(H₂O)₄] cluster units which develop around 4 axes. These units feature a central cubane-like tetramanganese(IV)-oxo moiety linked to eight peripheral manganese(III) centres by eight µ₃-O and four µ-acetato ligands. Twelve additional µ-acetates and four water ligands complete the Jahn–Teller distorted coordination sphere of the manganese(III) ions (Lis, 1980).

The relationship between tunnelling and molecular symmetry in (I) has recently become the focus of considerable interest, because the selection rules imposed by the S₄ crystallographic symmetry are not obeyed. For this reason, symmetry-breaking effects arising from crystal dislocations have been suggested (Mertes et al., 2001). Close examination of the structural data, however, suggests a possible mechanism for symmetry-lowering at the molecular level. Each cluster is in fact surrounded by four water and two acetic acid molecules of solvation. The latter are located between adjacent Mn₁₂ units in the ab plane and are disordered over two partially overlapping positions related by a twofold axis parallel to c. As confirmed by a very recent neutron diffraction study at LT (Langan et al., 2001), one of the acetate ligands (O6—O7—C3—C4) is involved in a strong hydrogen-bonding interaction with the disordered acetic acid molecule. Indeed, atom O6 and the neighbouring methyl atom C4 exhibit unusually large displacement parameters at RT compared with the remaining acetate ligands (Lis, 1980), possibly reflecting unresolved disorder.

To investigate this issue in more detail, we collected a new set of X-ray diffraction data at 83 (2) K. Preliminary structure refinement showed abnormal elongation of the displacement ellipsoids of atoms O6, C4 and, to a lesser extent, O7 and C3. We thus modelled the O6—O7—C3—C4 acetate ligand over two positions, A and B (Figs. 1 and 2). The resulting hydrogen-bonding geometry between atoms O15 and O6A [O15···O6A 2.687 (7) Å, H15···O6A 1.68 Å and O15—H15···O6A 169°] compares extremely well with that found in solid acetic acid at the same temperature (O···O' 2.624 Å, H···O' 1.628 Å and O—H···O' 164.9°; Reference?).

Notably, the coordination geometry of atoms Mn2 and Mn3 undergoes significant distortion upon hydrogen bonding, the Mn2—O6 and Mn3—O7 distances varying by -0.09 and 0.05 Å, respectively. Angular distortions are also meaningful, with O6A—Mn2—O6B 14.10 (14)° and O7A—Mn3ⁱ—O7B 6.8 (3)°.

These results definitely show that the disorder of the acetic acid molecule is supramolecularly transmitted to the Mn₁₂ units via a strong hydrogen-bonding interaction. Since the number (n) of hydrogen-bonded acetic acid molecules which surround each Mn₁₂ unit can, in principle, range from 0 to 4, up to six isomeric forms of the cluster can be envisaged. Two of them (n = 0 and 4) retain S₄ point-group symmetry, while the remaining isomers have either C₂ (n = 2, `trans') or C<sub>1</sub> (n = 1, 2, `cis', and 3) symmetry. Ordered layers of alternating n = 0 and 4 isomers would clearly preserve S₄ molecular symmetry, at the same time leading to doubled unit-cell vectors in the ab plane. Careful inspection of the diffraction pattern using a CCD device gave no hint as to the presence of a supercell, thus excluding an ordered structure in the ab plane. Nonaxial isomers must then be present in the lattice, which provides a possible explanation for the intriguing tunnelling behavior of (I) (Cornia et al., 2002).

S2. Experimental

Compound (I) was synthesized as described by Lis (1980). Crystals were obtained from solution in which solvent?

S3. Refinement

The space-group assignment based on RT data (I4) was confirmed at 83 (2) K by the Laue symmetry of the diffraction pattern, the systematic absences and the successful solution and refinement of the structure. An anisotropic model including all non-H atoms in the cluster, along with the crystallization water molecule, was used to determine the correct absolute structure. The R₁ and Flack parameters (Flack, 1983) were 0.0592 and 0.11 (3), respectively, compared with 0.0638 and 0.87 (4), respectively, for the inverted structure (x' = x, y' = y, z' = -z). A rigid-group refinement with isotropic displacement parameters, based on the molecular structure of acetic acid at the same temperature (Nahringbauer, 1970), was used for the disordered acetic acid of solvation. The two components (A and B) of the disordered acetate ligand were restrained to have the same geometry as O8—O9—C5—C6. The same isotropic displacement parameters were assigned to corresponding atoms in the two fragments, A and B. The final site occupancy factors were 0.457 (7) and 0.543 (7) for A and B, respectively. The H atoms of the coordinated water molecule (O12) were located in difference Fourier maps and refined isotropically with restrained O—H distances, while those of the extra-cluster water molecule (O13) were set in the positions determined by neutron diffraction (Langan et al., 2001). The H atoms in the methyl groups were treated as riding in the tetrahedral approximation with torsion angle refinement.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I) at 83 (2) K. The two positions occupied by the acetic acid molecule and by the O6—O7—C3—C4 acetate ligand are differentiated using solid and open bonds. For clarity, only the H atoms of acetic acid and water molecules are shown (small spheres). The network of hydrogen bonds is marked by dashed lines. Displacement ellipsoids are at the 50% probability level.
	Fig. 2. The coordination environment of atoms Mn2 and Mn3. Displacement ellipsoids are at the 50% probability level.

hexadeca-µ-acetato-tetraaquadodeca-µ₃-oxo-dodecamanganese acetic acid disolvate tetrahydrate

Crystal data

[Mn12O12(C2H3O2)16(H2O)4]·4H2O·2C2H4O2	Dx = 1.895 Mg m^−3
Mr = 2060.22	Melting point: not measured K
Tetragonal, I4	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I -4	Cell parameters from 70298 reflections
a = 17.1668 (3) Å	θ = 1.0–27.5°
c = 12.2545 (3) Å	µ = 2.13 mm^−1
V = 3611.39 (13) Å^3	T = 83 K
Z = 2	Parallelepiped, black
F(000) = 2072	0.18 × 0.12 × 0.08 mm

Data collection

Nonius KappaCCD area-detector diffractometer	4151 independent reflections
Radiation source: fine-focus sealed tube	3980 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −22→22
Tmin = 0.718, Tmax = 0.849	k = −22→22
24331 measured reflections	l = −15→15

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.030	w = 1/[σ^2(Fo^2) + (0.0379P)^2 + 2.657P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.073	(Δ/σ)max < 0.001
S = 1.13	Δρmax = 0.51 e Å^−3
4151 reflections	Δρmin = −0.57 e Å^−3
235 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
31 restraints	Extinction coefficient: 0.00236 (18)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1976 Friedel pairs Query
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.102 (16)

Special details

Experimental. Data collection was performed at the Centre de Diffractométrie, Université de Rennes, France. A crystal-to-detector distance of 25 mm was used and a total of 309 frames were recorded, using Δω 1° rotation scans, with exposure time = 40 sec/°.). 95 mm CCD camera on κ goniostat

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	−0.08339 (2)	0.01783 (2)	0.07815 (4)	0.01272 (10)
Mn2	−0.24182 (2)	0.04803 (2)	0.08026 (4)	0.01491 (10)
Mn3	−0.19841 (2)	−0.14079 (2)	0.01641 (3)	0.01604 (11)
O1	−0.07053 (10)	0.01528 (10)	−0.07593 (16)	0.0129 (4)
O2	−0.10585 (11)	−0.14810 (11)	−0.06681 (15)	0.0147 (4)
O3	−0.17552 (10)	−0.03871 (10)	0.06645 (15)	0.0142 (4)
O12	−0.26415 (15)	−0.10336 (14)	−0.1261 (2)	0.0315 (6)
H12A	−0.250 (3)	−0.126 (3)	−0.184 (3)	0.082 (15)*
H12B	−0.277 (3)	−0.0561 (15)	−0.131 (6)	0.082 (15)*
O13	−0.21629 (14)	−0.18889 (15)	−0.3008 (2)	0.0341 (6)
H13A	−0.1696	−0.2161	−0.2886	0.082*
H13B	−0.2450	−0.2200	−0.3346	0.082*
O4	−0.08534 (11)	0.01962 (11)	0.23458 (16)	0.0171 (4)
O5	−0.21272 (11)	0.04686 (12)	0.25772 (17)	0.0196 (4)
C1	−0.14510 (17)	0.03571 (16)	0.2929 (2)	0.0184 (6)
C2	−0.12864 (19)	0.04385 (19)	0.4134 (3)	0.0256 (6)
H2A	−0.0879	0.0069	0.4346	0.057 (4)*
H2B	−0.1762	0.0329	0.4548	0.057 (4)*
H2C	−0.1112	0.0971	0.4289	0.057 (4)*
O8	−0.33490 (11)	−0.01406 (12)	0.10130 (17)	0.0191 (4)
O9	−0.29783 (12)	−0.13967 (12)	0.09568 (19)	0.0235 (5)
C5	−0.34687 (16)	−0.08623 (16)	0.1120 (2)	0.0171 (5)
C6	−0.42692 (17)	−0.10966 (17)	0.1491 (3)	0.0239 (6)
H6A	−0.4390	−0.1618	0.1212	0.057 (4)*
H6B	−0.4652	−0.0723	0.1212	0.057 (4)*
H6C	−0.4287	−0.1102	0.2290	0.057 (4)*
O10	−0.30780 (12)	0.13681 (12)	0.1125 (2)	0.0269 (5)
O11	−0.24671 (12)	0.23385 (12)	0.0278 (2)	0.0246 (5)
C7	−0.30302 (16)	0.20626 (15)	0.0799 (2)	0.0171 (5)
C8	−0.36954 (17)	0.25892 (17)	0.1077 (2)	0.0218 (6)
H8A	−0.3749	0.2989	0.0511	0.057 (4)*
H8B	−0.3596	0.2840	0.1782	0.057 (4)*
H8C	−0.4177	0.2284	0.1120	0.057 (4)*
O6A	−0.2797 (3)	0.0690 (3)	−0.0832 (4)	0.0188 (6)*	0.457 (7)
O7A	−0.1875 (4)	0.1434 (4)	−0.1609 (6)	0.0201 (6)*	0.457 (7)
C3A	−0.2442 (4)	0.0945 (4)	−0.1654 (7)	0.0204 (8)*	0.457 (7)
C4A	−0.2673 (6)	0.0679 (5)	−0.2792 (6)	0.0363 (12)*	0.457 (7)
H4A1	−0.2253	0.0362	−0.3104	0.057 (4)*	0.457 (7)
H4A2	−0.2764	0.1134	−0.3256	0.057 (4)*	0.457 (7)
H4A3	−0.3150	0.0367	−0.2749	0.057 (4)*	0.457 (7)
O6B	−0.2596 (3)	0.0476 (3)	−0.0997 (3)	0.0188 (6)*	0.543 (7)
O7B	−0.1970 (3)	0.1547 (3)	−0.1572 (5)	0.0201 (6)*	0.543 (7)
C3B	−0.2293 (3)	0.0897 (4)	−0.1738 (6)	0.0204 (8)*	0.543 (7)
C4B	−0.2337 (5)	0.0578 (4)	−0.2869 (5)	0.0363 (12)*	0.543 (7)
H4B1	−0.2467	0.0998	−0.3378	0.057 (4)*	0.543 (7)
H4B2	−0.2739	0.0173	−0.2901	0.057 (4)*	0.543 (7)
H4B3	−0.1832	0.0352	−0.3069	0.057 (4)*	0.543 (7)
O14	−0.4148 (3)	−0.0726 (2)	−0.1212 (5)	0.0482 (14)*	0.50
O15	−0.4352 (3)	0.0537 (2)	−0.0962 (5)	0.0446 (13)*	0.50
H15	−0.3760	0.0558	−0.0997	0.053*	0.50
C9	−0.4605 (2)	−0.01792 (19)	−0.1119 (3)	0.0369 (16)*	0.50
C10	−0.5463 (2)	−0.0248 (3)	−0.1120 (7)	0.052 (2)*	0.50
H10A	−0.5618	−0.0696	−0.1567	0.077*	0.50
H10B	−0.5692	0.0228	−0.1424	0.077*	0.50
H10C	−0.5649	−0.0322	−0.0371	0.077*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01215 (19)	0.01262 (19)	0.01338 (18)	−0.00033 (14)	0.00068 (14)	−0.00004 (15)
Mn2	0.01247 (19)	0.0129 (2)	0.0194 (2)	0.00037 (14)	0.00188 (16)	0.00100 (16)
Mn3	0.0134 (2)	0.0136 (2)	0.0211 (2)	−0.00063 (16)	0.00259 (16)	−0.00320 (16)
O1	0.0129 (9)	0.0118 (8)	0.0139 (8)	0.0017 (7)	−0.0008 (7)	−0.0003 (8)
O2	0.0143 (9)	0.0121 (8)	0.0176 (9)	−0.0008 (7)	−0.0001 (8)	−0.0007 (8)
O3	0.0123 (8)	0.0145 (9)	0.0159 (9)	−0.0010 (7)	0.0004 (7)	−0.0003 (7)
O12	0.0353 (14)	0.0251 (12)	0.0341 (12)	0.0083 (10)	−0.0137 (10)	−0.0095 (10)
O13	0.0261 (12)	0.0397 (14)	0.0364 (13)	0.0027 (10)	−0.0095 (10)	−0.0137 (11)
O4	0.0182 (10)	0.0188 (10)	0.0144 (9)	−0.0016 (8)	0.0010 (7)	−0.0007 (7)
O5	0.0192 (10)	0.0191 (9)	0.0206 (10)	0.0004 (8)	0.0045 (8)	0.0000 (8)
C1	0.0217 (14)	0.0151 (13)	0.0183 (13)	−0.0021 (10)	0.0007 (11)	−0.0006 (10)
C2	0.0292 (16)	0.0302 (16)	0.0174 (13)	−0.0016 (12)	0.0017 (12)	−0.0028 (12)
O8	0.0156 (9)	0.0162 (9)	0.0256 (12)	0.0005 (7)	0.0029 (8)	0.0035 (8)
O9	0.0178 (10)	0.0185 (10)	0.0343 (12)	0.0007 (8)	0.0070 (9)	−0.0055 (9)
C5	0.0162 (13)	0.0196 (14)	0.0156 (12)	−0.0008 (11)	0.0011 (10)	0.0009 (10)
C6	0.0146 (14)	0.0193 (14)	0.0379 (17)	−0.0004 (11)	0.0079 (12)	0.0037 (13)
O10	0.0167 (10)	0.0176 (10)	0.0464 (14)	0.0049 (8)	0.0114 (9)	0.0079 (9)
O11	0.0201 (10)	0.0186 (10)	0.0352 (12)	0.0033 (8)	0.0084 (9)	0.0057 (9)
C7	0.0170 (12)	0.0174 (12)	0.0168 (12)	0.0022 (10)	0.0014 (11)	0.0000 (11)
C8	0.0220 (14)	0.0178 (14)	0.0256 (16)	0.0017 (11)	0.0036 (11)	0.0010 (11)

Geometric parameters (Å, º)

Mn1—Mn2	2.7687 (6)	C2—H2C	0.9800
Mn1—Mn1^i	2.8204 (7)	O8—C5	1.263 (3)
Mn1—Mn1^ii	2.9280 (8)	O9—C5	1.261 (3)
Mn1—O3	1.8611 (18)	C5—C6	1.502 (4)
Mn1—O2^iii	1.8804 (18)	C6—H6A	0.9800
Mn1—O1	1.902 (2)	C6—H6B	0.9800
Mn1—O1^i	1.9154 (18)	C6—H6C	0.9800
Mn1—O1^iii	1.9206 (17)	O10—C7	1.260 (3)
Mn1—O4	1.918 (2)	O11—C7	1.251 (4)
Mn2—O3	1.8818 (18)	C7—C8	1.496 (4)
Mn2—O2^iii	1.8975 (19)	C8—H8A	0.9800
Mn2—O8	1.938 (2)	C8—H8B	0.9800
Mn2—O10	1.940 (2)	C8—H8C	0.9800
Mn2—O6A	2.137 (5)	O6A—C3A	1.257 (9)
Mn2—O6B	2.227 (4)	O7A—C3A	1.286 (10)
Mn2—O5	2.231 (2)	C3A—C4A	1.520 (10)
Mn3—O2	1.8923 (19)	C4A—H4A1	0.9800
Mn3—O3	1.8977 (18)	C4A—H4A2	0.9800
Mn3—O9	1.964 (2)	C4A—H4A3	0.9800
Mn3—O11^i	1.993 (2)	O6B—C3B	1.271 (7)
Mn3—O7A^i	2.161 (7)	O7B—C3B	1.264 (8)
Mn3—O7B^i	2.114 (6)	C3B—C4B	1.492 (9)
Mn3—O12	2.177 (2)	C4B—H4B1	0.9800
O12—H12A	0.85 (2)	C4B—H4B2	0.9800
O12—H12B	0.843 (19)	C4B—H4B3	0.9800
O13—H13A	0.9396	O14—C9	1.2281
O13—H13B	0.8366	O15—C9	1.3188
O4—C1	1.280 (4)	O15—H15	1.0182
O5—C1	1.253 (4)	C9—C10	1.4781
C1—C2	1.510 (4)	C10—H10A	0.9800
C2—H2A	0.9800	C10—H10B	0.9800
C2—H2B	0.9800	C10—H10C	0.9800
Mn2—Mn1—Mn1^i	120.91 (2)	Mn3—O2—Mn2^i	122.84 (10)
Mn2—Mn1—Mn1^iii	122.47 (2)	Mn1—O3—Mn2	95.41 (8)
Mn1^i—Mn1—Mn1^iii	62.539 (17)	Mn1—O3—Mn3	133.04 (10)
Mn2—Mn1—Mn1^ii	178.61 (2)	Mn2—O3—Mn3	129.38 (10)
Mn1^i—Mn1—Mn1^ii	58.730 (9)	Mn3—O12—H12A	113 (4)
O3—Mn1—O2^iii	84.92 (8)	Mn3—O12—H12B	119 (5)
O3—Mn1—O1	90.59 (8)	H12A—O12—H12B	117 (6)
O2^iii—Mn1—O1	90.79 (8)	H13A—O13—H13B	105.3
O3—Mn1—O1^i	96.00 (8)	C1—O4—Mn1	125.11 (18)
O2^iii—Mn1—O1^i	174.79 (8)	C1—O5—Mn2	122.94 (18)
O1—Mn1—O1^i	84.08 (9)	O5—C1—O4	125.7 (3)
O3—Mn1—O4	94.04 (8)	O5—C1—C2	119.7 (3)
O2^iii—Mn1—O4	92.91 (8)	O4—C1—C2	114.6 (3)
O1—Mn1—O4	174.31 (8)	C1—C2—H2A	109.5
O1^i—Mn1—O4	92.14 (8)	C1—C2—H2B	109.5
O3—Mn1—O1^iii	173.75 (8)	C1—C2—H2C	109.5
O2^iii—Mn1—O1^iii	98.14 (8)	H2A—C2—H2B	109.5
O1—Mn1—O1^iii	83.94 (9)	H2A—C2—H2C	109.5
O1^i—Mn1—O1^iii	80.47 (8)	H2B—C2—H2C	109.5
O4—Mn1—O1^iii	91.26 (8)	C5—O8—Mn2	133.44 (19)
O3—Mn2—O2^iii	83.87 (8)	C5—O9—Mn3	131.74 (19)
O3—Mn2—O8	94.33 (8)	O9—C5—O8	126.1 (3)
O2^iii—Mn2—O8	176.66 (8)	O9—C5—C6	117.6 (2)
O3—Mn2—O10	173.35 (10)	O8—C5—C6	116.3 (2)
O2^iii—Mn2—O10	95.85 (8)	C5—C6—H6A	109.5
O8—Mn2—O10	85.61 (9)	C5—C6—H6B	109.5
O3—Mn2—O6A	103.47 (19)	C5—C6—H6C	109.5
O2^iii—Mn2—O6A	95.10 (13)	H6A—C6—H6B	109.5
O8—Mn2—O6A	88.05 (13)	H6A—C6—H6C	109.5
O10—Mn2—O6A	83.18 (19)	H6B—C6—H6C	109.5
O3—Mn2—O6B	89.50 (16)	C7—O10—Mn2	129.83 (19)
O2^iii—Mn2—O6B	91.83 (12)	C7—O11—Mn3^iii	136.72 (18)
O8—Mn2—O6B	90.97 (12)	O11—C7—O10	124.8 (2)
O10—Mn2—O6B	97.15 (16)	O11—C7—C8	118.5 (2)
O6A—Mn2—O6B	14.10 (14)	O10—C7—C8	116.7 (2)
O3—Mn2—O5	86.85 (8)	C7—C8—H8A	109.5
O2^iii—Mn2—O5	84.23 (8)	C7—C8—H8B	109.5
O8—Mn2—O5	92.86 (8)	C7—C8—H8C	109.5
O10—Mn2—O5	86.50 (9)	H8A—C8—H8B	109.5
O6A—Mn2—O5	169.54 (18)	H8A—C8—H8C	109.5
O6B—Mn2—O5	174.90 (15)	H8B—C8—H8C	109.5
O2—Mn3—O3	93.52 (8)	C3A—O6A—Mn2	131.4 (4)
O2—Mn3—O9	175.55 (9)	C3A—O7A—Mn3^iii	126.9 (6)
O3—Mn3—O9	90.64 (8)	O6A—C3A—O7A	124.2 (7)
O2—Mn3—O11^i	92.83 (8)	O6A—C3A—C4A	120.2 (7)
O3—Mn3—O11^i	173.62 (8)	O7A—C3A—C4A	115.7 (7)
O9—Mn3—O11^i	82.99 (9)	C3B—O6B—Mn2	130.5 (4)
O2—Mn3—O7B^i	96.42 (16)	C3B—O7B—Mn3^iii	130.2 (5)
O3—Mn3—O7B^i	94.84 (17)	O7B—C3B—O6B	124.6 (6)
O9—Mn3—O7B^i	84.77 (16)	O7B—C3B—C4B	119.7 (6)
O11^i—Mn3—O7B^i	85.05 (17)	O6B—C3B—C4B	115.7 (6)
O2—Mn3—O7A^i	92.89 (19)	C3B—C4B—H4B1	109.5
O3—Mn3—O7A^i	89.27 (18)	C3B—C4B—H4B2	109.5
O9—Mn3—O7A^i	88.73 (19)	C3B—C4B—H4B3	109.5
O11^i—Mn3—O7A^i	91.02 (19)	H4B1—C4B—H4B2	109.5
O7B^i—Mn3—O7A^i	6.8 (3)	H4B1—C4B—H4B3	109.5
O2—Mn3—O12	91.29 (9)	H4B2—C4B—H4B3	109.5
O3—Mn3—O12	95.40 (8)	C9—O15—H15	110.8
O9—Mn3—O12	86.76 (10)	O14—C9—O15	121.1
O11^i—Mn3—O12	83.85 (10)	O14—C9—C10	125.1
O7B^i—Mn3—O12	166.77 (16)	O15—C9—C10	113.8
O7A^i—Mn3—O12	173.54 (19)	C9—C10—H10A	109.5
Mn1—O1—Mn1^iii	95.28 (8)	C9—C10—H10B	109.5
Mn1—O1—Mn1^i	95.11 (8)	C9—C10—H10C	109.5
Mn1^iii—O1—Mn1^i	99.51 (8)	H10A—C10—H10B	109.5
Mn1^i—O2—Mn3	132.48 (10)	H10A—C10—H10C	109.5
Mn1^i—O2—Mn2^i	94.25 (8)	H10B—C10—H10C	109.5

Symmetry codes: (i) −y, x, −z; (ii) −x, −y, z; (iii) y, −x, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12a···O13	0.85 (4)	1.88 (5)	2.722 (4)	172 (4)
O12—H12b···O6A	0.84 (3)	2.23 (3)	3.016 (6)	156 (2)
O12—H12b···O6B	0.84 (3)	1.85 (3)	2.613 (5)	150 (2)
O13—H13a···O5^i	0.94	2.14	2.984 (3)	149
O13—H13b···O7A^iv	0.84	2.49	3.244 (7)	151
O13—H13b···O7B^iv	0.84	2.24	3.001 (6)	152
O13—H13b···O11^iv	0.84	2.46	3.114 (3)	135
O13—H13b···O9^v	0.84	2.66	3.214 (3)	125
O15—H15···O6A	1.02	1.68	2.687 (7)	169

Symmetry codes: (i) −y, x, −z; (iv) y−1/2, −x−1/2, −z−1/2; (v) −x−1/2, −y−1/2, z−1/2.